Porous polymer supported polyoxometalates

ABSTRACT

A composition for the destruction of chemical warfare agents and toxic industrial chemicals having a polyoxometalate (POM) attached to an amine, carboxylic acid, or ammonium substituted porous polymer. Also disclosed is a method for attaching a POM to an amine, carboxylic acid, or ammonium substituted porous polymer by (1) dissolving the POM in water or an organic solvent, adding the functionalized porous polymer, whereby the POM ionically attaches to the amine, carboxylic acid or ammonium group, or (2) heating the POM and functionalized polymer in the presence of a dehydrating agent whereby an imide bond is produced between the POM and the functionality on the porous polymer.

PRIORITY CLAIM

This Application claims priority from U.S. Provisional Application No. 61/541,151 filed on Sep. 30, 2011 by Matthew Laskoski, entitled “POROUS POLYMER SUPPORTED POLYOXOMETALATES,” the entire contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to polyoxometalates and, more specifically, to polyoxometalates attached to porous polymer substrates.

2. Description of the Prior Art

Polyoxometalates (POMs) have been used as oxidation, polymerization, and hydration catalysts for over 20 years. They have a very strong acidity approaching the superacid region, and are efficient oxidants, exhibiting fast reversible multi-electron redox transformations under mild conditions (Kozhevnikov, Chem. Rev., 98, 171-198 (1998)). These properties are advantageous for the catalytic destruction of chemical warfare agents (CWAs) and toxic industrial chemicals (TICs). For instance, the Fe^(III)[H(ONO₂)₂]PW₁₁O₃₉ ⁵⁻(POM) is known for its aerobic catalytic oxidation of HD (sulfur mustard) (Okun et al., J. of Mol. Cat. A: Chem., 246, 11-17 (2006)). The real-world performance of POMs for such applications, however, is often limited by the low surface areas of typical solid-state forms of this material, resulting in poor catalyst utilization. This limitation can be overcome by suspending the POMs into a polymer matrix. Unfortunately, the inability of the POM to stay suspended in the polymer over time leads to unpredictable catalytic activity. Such effects as mechanical strength and thermal and chemical stability are often difficult to realize by simple doping of POMs into polymer matrices. The current research is focused on maintaining the innate catalytic properties of POMs in the solid state after attaching POMs to a porous polymer. Covalently or ionically bound POMs will limit inherent aggregation while preserving long-term stable catalytic activity representative of the parent POM, with the added benefit of the polymer backbone which will allow the formation of films, coatings and composites.

BRIEF SUMMARY OF THE INVENTION

The present invention provides a composition for the destruction of chemical warfare agents and toxic industrial chemicals having a polyoxometalate (POM) attached to an amine, carboxylic acid, or ammonium substituted porous polymer. Also disclosed is a method for attaching a POM to an amine, carboxylic acid, or ammonium substituted porous polymer by (1) dissolving the POM in water or an organic solvent, adding the functionalized porous polymer, whereby the POM ionically attaches to the amine, carboxylic acid, or ammonium group, or (2) heating the POM and functionalized polymer in the presence of a dehydrating agent whereby an imide bond is produced between the POM and the functionality on the porous polymer.

The purpose of this invention is: (1) composition of matter identified as a polyoxometalate attached to a porous organic polymer substrate; and (2) general synthetic procedures for preparation of this class of material from a functionalized porous organic polymer and various inorganic polyoxometalates. Interest in such compositions of matter is driven primarily by highly active oxidation catalysts for use in the air based destruction of chemical warfare agents (CWAs) and toxic industrial chemicals (TICs).

These and other features and advantages of the invention, as well as the invention itself, will become better understood by reference to the following detailed description, appended claims, and accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic showing ionic attachment of polyoxometalates to a porous polymer.

FIG. 2 is a schematic showing covalent attachment of polyoxometalates to a porous polymer.

FIG. 3 is FTIR spectra of amine functionalized porous polystyrene beads (top) and H₅PV₂Mo₁₀O₄₀ attached to porous polystyrene beads (bottom).

FIG. 4 is the chemical structure for dimethylaminofluorene based PIM (DMAFN⁺ PIM).

FIG. 5 is the chemical structure for aminofluorene based PIM (AFN⁺ PIM).

FIG. 6 is the chemical structure for dimethylaminomethylene benzene based PIM (DMAMBN⁺ PIM).

FIG. 7 is the chemical structure for ethanoanthracene based PIM (EATBN⁺ PIM).

FIG. 8 is the chemical structure for carboxylated PIM-1 (C-PIM-1).

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a new composition of matter (and corresponding method of preparation) for previously unknown functional materials that can be employed as oxidation catalysts for the destruction of CWAs or TICs. These new high surface area POM-containing polymeric materials have better performance toward catalytic oxidation reactions when compared to unsupported POMs with the added benefit of having them permanently attached on a lightweight, processable polymer substrate. The materials of the present invention are the first described for the attachment of a polyoxometalate to a porous organic polymer substrate functionalized with amine, carboxylic acid, or ammonium groups. Another chief advantage of this procedure is that is scalable to large quantities.

The present invention provides a general procedure for the attachment of polyoxometalates (POMs) to an amine, carboxylic acid, or ammonium substituted porous polymer such as functionalized polystyrene (see FIG. 1). The attachment can be performed in two ways. First, the POM is dissolved in water or an organic solvent and stirred with the functionalized porous polymer whereby the POM ionically attaches to the amine, carboxylic acid, or ammonium group (See FIG. 1. The color of the beads is green only when the POM is attached to the polymer). Second, the POM and the amine functionalized polymer are heated in the presence of a dehydrating agent (such as N,N′-dicyclohexylcarbodiimide (e.g. DCC)) whereby an imide bond is produced between a metal center in the POM and the amine functionality on the polymer (see FIG. 2). The functionalized polymers that can be used in this case comprise porous polystyrenes (PPS) (available through Sigma-Aldrich), polymers of intrinsic microporosity (Ghanem et al., Macromolecules, 43, 5287-5294 (2010)), conjugated microporous polymers (Dawson et al., Macromolecules, 42, 8809-8816 (2009)) and/or any other porous polymer that can be functionalized with an amine, carboxylic acid, or ammonium group.

In both the ionic and covalent attachment schemes, the presence of the POM on the polymer was determined by FTIR spectroscopy. FIG. 3 shows the IR region from 2500 to 450 cm⁻¹, and three distinct peaks can be seen in the spectra for a sample, where H₅PV₂Mo₁₀O₄₀ was attached to PSS beads (bottom), at approximately 1046, 939 and 878 cm⁻¹ (circled in bottom plot). This is consistent with the location of the M=O stretches in the parent POM. In addition, the sample took up an appreciable amount of weight (˜60%) indicating that the POM was incorporated into the polymer structure.

EXAMPLE 1 Formulation of Polymer of Intrinsic Microporosity (DMAFN⁺ PIM) and the POM (K₆CuPW₁₁O₃₉) Made with Cu(NO₃)₂

FIG. 4 shows the chemical structure for dimethylaminofluorene based PIM (DMAFN⁺ PIM).

K₇PW₁₁O₃₉ (0.100 g, 0.0344 mmol) was dissolved in 3 mL of hot water and Cu(NO₃)₂ (0.010 g, 0.041 mmol) was added with vigorous stirring. To this solution was added the DMAFN⁺ PIM (0.500 g) and 2 mL of CH₃CN. Gentle heating to 60° C. for 10 min produced a suspension and the mixture was allowed to cool and stiffing was continued for an additional 2 h. The solvent was removed and 0.590 g of a grey powder was recovered after vacuum drying at 50° C. The presence of the POM on the PIM was confirmed by observing the P—O, W—O and W—O—W peaks in the FTIR at approximately 1050, 930 and 820, respectively.

EXAMPLE 2 Formulation of Polymer of Intrinsic Microporosity (DMAFN⁺ PIM) and the POM (K₆FePW₁₁O₃₉) Made with Fe(NO₃)₃.

K₇PW₁₁O₃₉ (0.100 g, 0.0344 mmol) was dissolved in 3 mL of hot water and the DMAFN⁺ PIM (0.100 g) in 2 mL of CH₃CN was added resulting in a cloudy solution. Fe(NO₃)₃ (0.004 g, 0.010 mmol) was added with vigorous stirring and the solution was allowed to stir for 1 h. The solvent was removed and 95 mg of a red powder was recovered after vacuum drying at 50° C. The presence of the POM on the PIM was confirmed by observing the P—O, W—O and W—O—W peaks in the FTIR at approximately 1050, 930 and 820, respectively.

EXAMPLE 3 Formulation of Polymer of Intrinsic Microporosity (DMAFN⁺ PIM) and the POM (H₅PV₂Mo₁₁O₄₀)

H₅PV₂Mo₁₀O₄₀ (0.050 g, 0.029 mmol) was dissolved in 3 mL of CH₃CN and the DMAFN⁺ PIM (0.250 g) in 2 mL of CH₃CN was added resulting in a cloudy solution. 10 mg of Tetrabutylammonium tribromide (TBABr₃) and Cu(NO₃)₃ (0.020 g, 0.083 mmol) were added with vigorous stiffing and the solution was allowed to stir for 1 h. The solvent was removed and 295 mg of an orange powder was recovered after vacuum drying at 50° C. The presence of the POM on the PIM was confirmed by observing the P—O, Mo—O and Mo—O—Mo peaks in the FTIR at approximately 1046, 939 and 878 cm⁻¹, respectively.

EXAMPLE 4 Formulation of Polymer of Intrinsic Microporosity (DMAFN⁺ PIM) and the POM (K₁₂Cu₃(PW₁₁O₃₄)₂) Made with Cu(NO₃)₂

K₁₂Cu₃(PW₁₁O₃₄)₂ (0.050 g, 0.010 mmol) was dissolved in 1 mL of H₂O and the DMAFN⁺ PIM (0.250 g) in 2 mL of CH₃CN was added resulting in a cloudy solution. The solution was allowed to stir for 1 h, the solvent was removed and 285 mg of a grey powder was recovered after vacuum drying at 50° C. The presence of the POM on the PIM was confirmed by observing the P—O, W—O and W—O—W peaks in the FTIR at approximately 1050, 930 and 820, respectively.

EXAMPLE 5 Formulation of Polymer of Intrinsic Microporosity (DMAFN⁺ PIM) and the POM (K₉(Fe(OH)₂)₃(PW₁₁O₃₄)₂) Made with Fe(NO₃)₂

K₉(Fe(OH)₂)₃(PW₁₁O₃₄)₂ (0.050 g, 0.010 mmol) was dissolved in 1 mL of H₂O and the DMAFN⁺ PIM (0.250 g) in 2 mL of CH₃CN was added resulting in a cloudy solution. The solution was allowed to stir for 1 h, the solvent was removed and 290 mg of an orange powder was recovered after vacuum drying at 50° C. The presence of the POM on the PIM was confirmed by observing the P—O, W—O and W—O—W peaks in the FTIR at approximately 1050, 930 and 820, respectively.

EXAMPLE 6 Formulation of Polymer of Intrinsic Microporosity (DMAFN⁺ PIM) and the POM (K₁₂Fe₃(PW₁₁O₃₄)₂) Made with FeBr₃

K₁₂Fe₃(PW₁₁O₃₄)₂ (0.050 g, 0.010 mmol) was dissolved in 1 mL of H₂O and the DMAFN⁺ PIM (0.250 g) in 2 mL of CH₃CN was added resulting in a cloudy solution. The solution was allowed to stir for 1 h, the solvent was removed and 280 mg of an orange powder was recovered after vacuum drying at 50° C. The presence of the POM on the PIM was confirmed by observing the P—O, W—O and W—O—W peaks in the FTIR at approximately 1050, 930 and 820, respectively.

EXAMPLE 7 Formulation of Polymer of Intrinsic Microporosity (DMAFN⁺ PIM) and the POM (K₁₂Cu₃(PW₁₁O₃₄)₂) Made with Cu(NO₃)₂ and the POM (K₁₂Fe₃(PW₁₁O₃₄)₂) Made with FeBr₃

K₁₂Cu₃(PW₁₁O₃₄)₂ (0.050 g, 0.010 mmol) and K₁₂Fe₃(PW₁₁O₃₄)₂ (0.050 g, 0.010 mmol) were dissolved in 2 mL of H₂O and the DMAFN⁺ PIM (0.250 g) in 2 mL of CH₃CN was added resulting in a cloudy solution. The was solution allowed to stir for 1 h, the solvent removed and 280 mg of a dark red powder was recovered after vacuum drying at 50° C. The presence of the POMs on the PIM was confirmed by observing the P—O, W—O and W—O—W peaks in the FTIR at approximately 1050, 930 and 820, respectively.

EXAMPLE 8 Formulation of Porous Amine Functionalized Polystyrene (PAFP) and the POM H₅PV₂Mo₁₀O₄₀

Porous Amine Functionalized Polystyrene (PAFP)—(Aminomethyl)polystyrene, macroporous, 30-60 mesh, extent of labeling: 1.5-3.0 mmol/g loading available through Aldrich.

H₅PV₂Mo₁₀O₄₀. (239 mg, 0.136 mmol) was dissolved in 2 mL of CH₃CN and the PAFP (326 mg) was added and the resulting suspension (PAFP beads did not dissolve) was stirred for 16 h. The solution gradually turned clear and the PAFP beads were filtered off, washed with CH₃CN and dried to yield 525 mg of green colored PAFP beads. The presence of the POMs on the PIM was confirmed by observing the P—O, Mo—O and Mo—O—Mo peaks in the FTIR at approximately 1046, 939 and 878 cm⁻¹(See FIG. 1).

EXAMPLE 9 Covalent Attachment of the POM ([(C₄H₉)N]₂ Mo₆O₁₉) to the Porous Amine Functionalized Polystyrene (PAFP)

[(C₄H₉)N]₂ Mo₆O₁₉ (820 mg, 0.698 mmol) was dissolved in 25 mL of CH₃CN and the PAFP (200 mg was added and the resulting suspension (PAFP beads did not dissolve). N,N′-Dicyclohexylcarbodiimide (140 mg, 0.680 mmol) was added and the suspension heated to 75° C. overnight (16 h). The reaction was filtered and washed with acetone and the coated beads dried to yield 260 mg of material (60 mg POM supported). The presence of the POMs on the PIM was confirmed by observing the P—O, Mo—O and Mo—O—Mo peaks in the FTIR at approximately 1046, 939 and 878 cm⁻¹.

EXAMPLE 10 Formulation of Polymer of Intrinsic Microporosity (AFN⁺ PIM) and the POM (H₅PV₂Mo₁₀O₄₀)

FIG. 5 shows the chemical structure for aminofluorene based PIM (AFN⁺ PIM).

H₅PV₂Mo₁₀O₄₀ (50 mg, 0.028 mmol) was dissolved in 3 mL of CH₃CN and the AFN⁺ PIM (25 mg) was added with vigorous stirring (the PIM did not dissolve). Following stirring for 16 h the suspension was filtered, washed with CH₃CN and the POM supported PIM recovered (37 mg) as an orange solid. The presence of the POM on the PIM was confirmed by observing the P—O, Mo—O and Mo—O—Mo peaks in the FTIR at approximately 1046, 939 and 878 cm⁻¹.

EXAMPLE 11 Formulation of Polymer of Intrinsic Microporosity (DMAMBN+ PIM) and the POM (H₅PV₂Mo₁₀O₄₀)

FIG. 6 shows the chemical structure for dimethylaminomethylene benzene based PIM (DMAMBN⁺ PIM)

H₅PV₂Mo₁₀O₄₀ (100 mg, 0.057 mmol) was dissolved in 3 mL of H₂O and separately the DMAMBN+ PIM (25 mg) was dissolved in 3 mL of hot water. The two solutions were combined with vigorous stirring resulting in the immediate precipitation of the PIM-POM hybrid. The precipitate was filtered, washed with water and CH₃CN and the resulting powder was dried. A green solid (375 mg) was recovered and the presence of the POM on the PIM was confirmed by observing the P—O, Mo—O and Mo—O—Mo peaks in the FTIR at approximately 1046, 939 and 878 cm⁻¹.

EXAMPLE 12 Formulation of Polymer of Intrinsic Microporosity (DMAMBN⁺ PIM) and the POM (K₆CuPW₁₁O₃₉) Made with Cu(NO₃)₂

K₇PW₁₁O₃₉ (0.100 g, 0.0344 mmol) was dissolved in 3 mL of hot water and Cu(NO₃)₂ (0.010 g, 0.041 mmol) was added with vigorous stirring. To this solution was added the DMAMBN+ PIM (0.130 mg) dissolved in 2 mL of H₂O. Immediate precipitation of the PIM-POM hybrid was observed. The precipitate was filtered after 10 min of stiffing, washed with water and CH₃CN and the resulting powder was dried. An orange solid (271 mg) was recovered and the presence of the POM on the PIM was confirmed by observing the P—O, W—O and W—O—W peaks in the FTIR at approximately 1050, 930 and 820, respectively.

EXAMPLE 13 Formulation of Polymer of Intrinsic Microporosity (EATBN⁺ PIM) and the POM (K₆CuPW₁₁O₃₉) Made with Cu(NO₃)₂

FIG. 7 shows the chemical structure for ethanoanthracene based PIM (EATBN⁺ PIM).

K₇PW₁₁O₃₉ (0.010 g, 0.0034 mmol) was dissolved in 3 mL of hot water and Cu(NO₃)₂ (0.001 g, 0.004 mmol) was added with vigorous stirring. To this solution was added the EATBN⁺ PIM (50 mg) in 1 mL of CH₃CN. Gentle heating to 60° C. for 10 min produced a suspension and the mixture was allowed to cool. Stiffing was continued for an additional 2 h. The solvent was removed and 58 mg of an orange powder was recovered after vacuum drying at 50° C. The presence of the POM on the PIM was confirmed by observing the P—O, W—O and W—O—W peaks in the FTIR at approximately 1050, 930 and 820, respectively.

EXAMPLE 14 Formulation of Polymer of Intrinsic Microporosity (EATBN⁺ PIM) and the POM (K₆FePW₁₁O₃₉) Made with Fe(NO₃)₃

K₇FePW₁₁O₃₉ (0.025 g, 0.0085 mmol) was dissolved in 3 mL of hot water and the EATBN⁺ PIM (0.100 g) in 2 mL of CH₃CN was added resulting in a cloudy solution. Fe(NO₃)₃ (0.004 g, 0.010 mmol) was then added with vigorous stirring and the resulting solution was allowed to stir for 1 h. The solvent was removed and 115 mg of a red powder was recovered after vacuum drying at 50° C. The presence of the POM on the PIM was confirmed by observing the P—O, W—O and W—O—W peaks in the FTIR at approximately 1050, 930 and 820, respectively.

EXAMPLE 15 Formulation of Polymer of Intrinsic Microporosity (EATBN⁺ PIM) and the POM (K₉(Fe(OH)₂)₃(PW₁₁O₃₄)₂) Made with Fe(NO₃)₂

K₉(Fe(OH)₂)₃(PW₁₁O₃₄)₂ (0.070 g, 0.014 mmol) was dissolved in 3 mL of hot water and to this solution was added the EATBN⁺ PIM (65 mg) in 1 mL of CH₃CN. Gentle heating to 60° C. for 10 min produced a suspension and the mixture was allowed to cool. Stirring was continued for an additional 2 h. The solvent was removed and 90 mg of an orange powder was recovered after vacuum drying at 50° C. The presence of the POM on the PIM was confirmed by observing the P—O, W—O and W—O—W peaks in the FTIR at approximately 1050, 930 and 820, respectively.

EXAMPLE 16 Formulation of Polymer of Intrinsic Microporosity and the POM (H₅PV₂Mo₁₀O₄₀)

H₅PV₂Mo₁₀O₄₀ (50 mg, 0.028 mmol) was dissolved in 3 mL of CH₃CN and the EATBN⁺ PIM (35 mg) was added with vigorous stirring (the PIM did not dissolve). Following stirring for 16 h, the suspension was filtered, washed with CH₃CN and the POM supported PIM was recovered (48 mg) as an orange solid. The presence of the POM on the PIM was confirmed by observing the P—O, Mo—O and Mo—O—Mo peaks in the FTIR at approximately 1046, 939 and 878 cm⁻¹.

EXAMPLE 17 Formulation of Polymer of Intrinsic Microporosity (C-PIM-1) and the POM (H₅PV₂Mo₁₀O₄₀)

FIG. 8 shows the chemical structure for carboxylated PIM-1 (C-PIM-1).

H₅PV₂Mo₁₀O₄₀ (50 mg, 0.028 mmol) was dissolved in 3 mL of CH₃CN and the C-PIM-1 (42 mg) (carboxylic acid containing PIM) was added with vigorous stirring (the PIM did not dissolve). Following stirring for 16 h, the suspension was filtered, washed with CH₃CN and the POM supported PIM was recovered (53 mg) as an orange solid. The presence of the POM on the PIM was confirmed by observing the P—O, Mo—O and Mo—O—Mo peaks in the FTIR at approximately 1046, 939 and 878 cm⁻¹.

EXAMPLE 18 Catalytic Oxidation of 2-chloroethylethylsulfide (CEES) to 2-chloroethylethylsulfoxide (CEESO) Using DMAFN⁺ PIM:K₅CuPW₁₁O₃₉POM Mixture

49 mg, 0.0037 mmol POM, of Example 1 was weighed into a 20 mL scintillation vial and 2 mL of anhydrous CH₃CN was added. To the suspension was added 10 mg of tetrabutylammonium nitrate (TBANO₃) and 10 mg of tetrabutylammonium bromide (TBABr) and the color of the reaction mixture turned orange. After 10 min of vigorous stiffing CEES (0.1 mL, 0.862 mmol) was added and the vial capped with a septa with a needle to ensure sufficient air availability. The reaction was monitored for 22 h with the results listed in Table 1.

TABLE 1 Results for Oxidation reaction of Example 18. POM (mol) % conversion Time (h) TOF TON 0.000003 47 1 120 120 0.000003 52 4 33 132 0.000003 55 22 6 140

EXAMPLE 19 Catalytic Oxidation of 2-chloroethylethylsulfide (CEES) to 2-chloroethylethylsulfoxide (CEESO) Using DMAFN⁺ PIM:K₅CuPW₁₁O₃₉ POM Mixture and Cu(OTf)₂/Cu(NO₃)₂

49 mg, 0.002 mmol POM, of Example 1 was weighed into a 20 mL scintillation vial and 2 mL of anhydrous CH₃CN was added. To the suspension was added 6 mg of tetrabutylammonium nitrate (TBANO₃) and 6 mg of tetrabutylammonium bromide (TBABr) and the color of the reaction mixture turned orange. Next, a 0.5 mL aliquot of a 15 mM Cu(NO₃)₂:22.5 mM Cu(OTf)₂ solution in CH₃CN was added and the mixture turned yellow. After 10 min of vigorous stiffing CEES (0.1 mL, 0.862 mmol) was added and the vial capped with a septa with a needle to ensure sufficient air availability. The reaction was monitored for 100 h with the results listed in Table 2.

TABLE 2 Results for oxidation reaction of Example 19. POM (mol) % conversion Time (h) TOF TON 0.0000016 48 1 229 229 0.0000016 60 22.5 13 287 0.0000016 68 100 3 325

EXAMPLE 20 Catalytic Oxidation of 2-chloroethylethylsulfide (CEES) to 2-chloroethylethylsulfoxide (CEESO) Using DMAFN⁺ PIM:K₅CuPW₁₁O₃₉ POM Mixture with Low Catalyst Loading

6 mg, 0.00045 mmol POM, of Example 1 was weighed into a 20 mL scintillation vial and 2 mL of anhydrous CH₃CN was added. To the suspension was added 6 mg of tetrabutylammonium nitrate (TBANO₃) and 6 mg of tetrabutylammonium bromide (TBABr) and the color of the reaction mixture turned orange. After 1 min of vigorous stirring CEES (0.1 mL, 0.862 mmol) was added and the vial capped with a septa with a needle to ensure sufficient air availability. The reaction was monitored for 96 h with the results listed in Table 3.

TABLE 3 Results for oxidation reaction of Example 20. POM (mol) % conversion Time (h) TOF TON 0.00000036 7 1 149 149 0.00000036 11 18.5 13 234 0.00000036 18 96 4 382

EXAMPLE 21 Catalytic Oxidation of 2-chloroethylethylsulfide (CEES) to 2-chloroethylethylsulfoxide (CEESO) Using DMAFN⁺ PIM:K₅FePW₁₁O₃₉ POM Mixture

22 mg, 0.0018 mmol POM, of Example 5 was weighed into a 20 mL scintillation vial and 2 mL of anhydrous CH₃CN was added. To the suspension was added 8 mg of tetrabutylammonium nitrate (TBANO₃) and 9 mg of tetrabutylammonium bromide (TBABr). After 10 min of vigorous stiffing CEES (0.1 mL, 0.862 mmol) was added and the vial capped with a septa with a needle to ensure sufficient air availability. The reaction was monitored for 22 h with the results listed in Table 4.

TABLE 4 Results for Oxidation reaction of Example 21. POM (mol) % conversion Time (h) TOF TON 0.0000018 20 1 85 85 0.0000018 25 17 6 106 0.0000018 26 22 5 110

EXAMPLE 22 Catalytic Oxidation of 2-chloroethylethylsulfide (CEES) to 2-chloroethylethylsulfoxide (CEESO) Using a DMAFN⁺PIM:K₅CuPW₁₁O₃₉ POM and a DMAFN⁺ PIM:K₅FePW₁₁O₃₉ POM Mixture

18 mg, 0.0014 mmol POM, Example 1 and (20 mg, 0.0016 mmol POM) of Example 5 was weighed into a 20 mL scintillation vial and 2 mL of anhydrous CH₃CN was added. To the suspension was added 10 mg of tetrabutylammonium nitrate (TBANO₃) and 10 mg of tetrabutylammonium bromide (TBABr). After 10 min of vigorous stiffing CEES (0.1 mL, 0.862 mmol) was added and the vial capped with a septa with a needle to ensure sufficient air availability. The reaction was monitored for 101 h with the results listed in Table 5.

TABLE 5 Results for Oxidation reaction of Example 22. POM (mol) % conversion Time (h) TOF TON 0.0000026 42 1 123 123 0.0000026 48 23.5 6 141 0.0000026 54 101 2 159

EXAMPLE 23 Catalytic Oxidation of 2-chloroethylethylsulfide (CEES) to 2-chloroethylethylsulfoxide (CEESO) Using a DMAFN⁺ PIM: K₉Cu₃(PW₁₁O₃₄)₂ POM

32 mg, 0.0011 mmol POM, Example 1 and (20 mg, 0.0016 mmol POM) of Example 5 was weighed into a 20 mL scintillation vial and 2 mL of anhydrous CH₃CN was added. To the suspension was added 9 mg of tetrabutylammonium nitrate (TBANO₃) and 9 mg of tetrabutylammonium bromide (TBABr). After 10 min of vigorous stiffing CEES (0.1 mL, 0.862 mmol) was added and the vial capped with a septa with a needle to ensure sufficient air availability. The reaction was monitored for 76 h with the results listed in Table 6.

TABLE 6 Results for Oxidation reaction of Example 23. POM (mol) % conversion Time (h) TOF TON 0.00000109 21 2 74 147 0.00000109 76 0 0

The above descriptions are those of the preferred embodiments of the invention. Various modifications and variations are possible in light of the above teachings without departing from the spirit and broader aspects of the invention. It is therefore to be understood that the claimed invention may be practiced otherwise than as specifically described. Any references to claim elements in the singular, for example, using the articles “a,” “an,” “the,” or “said,” is not to be construed as limiting the element to the singular. 

What is claimed as new and desired to be protected by Letters Patent of the United States is:
 1. A method for attaching polyoxometalates (POMs) to an amine, carboxylic acid, or ammonium substituted polymer, comprising: dissolving the POM in water or an organic solvent, wherein the POM has the formula [K₆XPW₁₁O₃₉], wherein X is selected from Cu and Fe; and adding the functionalized polymer to make a porous polymer product; wherein the POM ionically attaches to the amine, carboxylic acid, or ammonium group.
 2. A method for attaching polyoxometalates (POMs) to an amine, carboxylic acid, or ammonium substituted polymer, comprising: dissolving the POM in water or an organic solvent, wherein the POM has the formula [K₁₂X₃(PW₁₁O₃₄)₂], wherein X is selected from Cu and Fe; and adding the functionalized polymer to make a porous polymer product; wherein the POM ionically attaches to the amine, carboxylic acid, or ammonium group.
 3. A method for attaching polyoxometalates (POMs) to an amine, carboxylic acid, or ammonium substituted polymer, comprising: dissolving the POM in water or an organic solvent, wherein the POM has the formula [K₉(Fe(OH)₂)₃(PW₁₁O₃₄)₂]; and adding the functionalized polymer to make a porous polymer product; wherein the POM ionically attaches to the amine, carboxylic acid, or ammonium group.
 4. A method for attaching polyoxometalates (POMs) to an amine, carboxylic acid, or ammonium substituted polymer, comprising: dissolving the POM in water or an organic solvent, wherein the POM has the formula [((C₄H₉)N)₂Mo₆O₁₉]; and adding the functionalized polymer to make a porous polymer product; wherein the POM ionically attaches to the amine, carboxylic acid, or ammonium group. 